Process for halogenating aminoanthraquinone compounds



Patented: Jan. 8, 19 35 pounds in which the amino group may be unsub v PROCESS eanness-mm. 14m n "Wimam" mfl'ws'refl eiiqki, essi gnor to i E. I. du Pont de Nemoillfs &;o m11 ny, Wfln'iington, Del., a, corporation for halogenating amino-anthraquinqne stituted, substituted; or' -ihwhich it may be one @fii h em i he r q rine- 1; :1 .1 Itis known that anthraquinone compounds m b h e a d in the P nce il zi lytie qu soi fi m Q Q Q MZI JZ W amounts of aluminum or iron chloride action proceeds-in a smoothwlandeasily co trolin" m ins ne si nitmben ne may ense a the medium carsolvent whichlthe halogenation-v 1113301136 carriedout. 1 "many 9t theselprocesses however, in which, the starting materi-alor final halogenated product ;is not. soluble the nitro}.

" benzene, thehalogenationi often hardtog con trol to-avoid the forrnationpfi isomeric or; higher halogenated bodies. Furthermore, relatively high; temperatures are often necessary tojforcefthe:

reaction to-r completion, and t s also tendsnto produce isomeric bcdies, wh;icl;1umustthen be sepie t' ib 'e s re temnewi I have now; ioundIthat-Tthese nltrogencontain-l nea re e tsmr nd vm r* m o ated at relatively low temperatures and the re s t e .rm s Qb in -morep re form mass, at least-to a large degreenin.solutionfl I have discovered that by the use: oLrelati-vel arge 1 lable manner. Theserlar-e quantities alsoappean t9 e t be marke d t flue e n? th halogenation givinga product containing a. min

imum amountofisomers and h igherl. halogena tion. compounds; q

v {The amount oi aluminum be'used to obtain these improved re imens. pends upon the relative ,sdlubility of amino compounds and their halogenation products in the metallic 1 chloride-nitrobenzene mixture,

Where the {amine is relatively insoluble in nitricbenzene, larger quantities of aluminu de are required to put itih somuomgm general;

[ and in all such cases a marked impr'ovementfin' 'ated'x It is "desirable that -suflicient aluminum amounts approximating molecular quenutiespf aluminum chloride and gamino -anthraquinone compounds have been foundtogive goodife'sults,

yie d and qua-11w f h ifitime e el tnt rl= uct is obtained over the use of1a1umin h1 on the anthraquinone compound -being.;- halog enchloride in conjunction withnitrobcnzene should be used to retain; the amino anthraquinone and reaction products in solution FatnI'OUHI temperae tare. 1 in It is believed that this peculiai efiect is; obtairfed due to" a temporary: combination 'o'fx'zthe anfino bodiwith the complex thatiorms by the ntainsv 23.7 C12.

tett n; 5i""sl mming mbfiaerwth. meets-e,

eefire t h-lw dein in d'to b iilted le any manner ;-by the correctness or inconrectnessf otthis,theorx.g n I ventiqn The parts .us'ed 'are weight. i

e in le am a e 2 1 e zfi r Example I Charge intov800 parts-tr dry nitrobenzene, 5b

parts ofisulphurylchloride inf2 parts; Theitem- 'perature will rise to 40%5" C. .aftereach 'addie tiorrnt-Theh maintain at-40' G-sforciihours and pour the contents into cold waterand remove the nitrobenzene by steam distillation. Filter the insoluble matter and 'washfree of salt.

stir this red-$0111. 'tion for? i i hou r" at -30 C. and addi then 70 11.21%mcombined chlorine and consistspof li-amije no-Aeeh-lor-anthraquinone." From to" 1 :part

hour andthen add in.2 portions 14 parts of sulphuryl chloride so that-the temperatureri'ses test s; Stir at 40"! for 3, hours and pour the whole into cold water. Remove the prepared solution" as. L20llpar$ of nitrobenzene with steamy The isolated product 1 gon s s,

Diss lve 1 0 parts of aluminumfchlorideain 200 parts of nitrobenzene and ;add' 20 partSiOf 1,5-

} diamino-anthraquinone.

user-rule violetg solution a hour and add 24 parts of sulphuryl chloride inntwo portions so thatfthe' temperature goes :up to: 45 "C.@Sti1: at 40 C, for 3 hours, pour into cold water and steam distil. The product consists mostly of 1,5-diamino-4=,8-dichlor=anthraquinone. It con- (Theory-23.15%.) a

nitrobenzene and parts of aluminum chloride, '50 parts of 1,1'-dianthraquinone imine. 1

Stir the blue solution for /;hourand add nat -25+30F 0., 32 parts of i-sulphuryl chlorides 1 Heat toi40 and keep-at 40for 12 hours; pour into ccldwaterandsteam distiland isolate The stitutesi ljy-dichloro-1,1"-dianthraquinone imine.

I I Example. 5

ferric chloride and "100 part offbaminmamhrw.

quinone'. r.

Stir the brown solution .for /2 hour add at 40 C. Then pour into cold water and isolate as per Example 1. r

Example 6 I'repare a solution of 50 parts of I-amino-anthraquinone in 300 parts of -nitrobenz'ene'and parts ofaluminum chloride (as explained in 'Example '1), Heat to 45-50"and pass in -parts.

The chlorine is absorbed very of chlorine ga s r readily. Then dilute with cold water and isolate,

The obtained chlor-amino-anthraquinone identical with Example 1.

. f met I Add 80 parts of bromine'toa prepared solu-' tion of 100 parts' of 1-amino-anthraquinone in 800 parts of nitrobenzene and parts of aluminum'chloride and'heat to 40 0., maintain at this temperature'for 2 hours and-steam distil.

The isolated product consists mostly of v1-ami-- no-2-brom-anthraquinone, as "itigi'ves. in'dan-' Erample; 9

j Chlorinate ZO parts, of indanthrone the same way as outlined in Example 8. A dichloro indan throne is obtained which'resembles in itsj'proper ties and behavior the.3,3' -dichloro-indanthrone.

Example. 10

' Dissolve 20 parts of 2-amino-anthraquinone in 200 parts of nitrobenzene and 10 parts of alumi num chloride. Stir hour and add 12 parts sulphuryl-"chloride.

1 Stir at roomtemperature for 4 hours: and stea distil the whole free of nitrobenzen'e.

"The obtained product consists' mostly-of 1-chlor-2-amino-anthraquinone 'which may be obtained in pure form by fractional crystallization from'sulphuricacid." J

' Example 11 Add to a prepared solution of 80 parts of nitro-'- benzene and 5v parts of aluminum chloride, 10

, parts of l-amino-2- methyl-anthraquinone.

v r I Example 12 v Chlorinate 20 parts of 8-amino-2,l -acridone in 200 parts of nitrobenzene and 10 parts of alumi- :rlum chloride with 8 parts of sulphuryl chloride Add to 500 Parts of mtrobenzene, 25 Parts of Yatroorn temperature ,for 4 hours and isolate as sl r i "The new compound is most probably S-amino- 5-chlor-2,1-acridone.

. Example 13 Dissolve 10 parts of Bzl-amino-benzanthrone in 100' parts of nitrobenzene and 5 parts of aluminum chloride and add 7 parts of sulphuryl chloride.

Keep at 2025 for 12-16 hours and isolate in the above described manner.

m'onochlor-monoamino benzanthrone is the resulting compound.

I f 5 Examp 14- l I Add 5.6 parts of anhydrous aluminum chloride to 100 parts of nitrobenzol. Stir for twenty minutes. Then add- 10 parts of l-methylamino-anthraquinone'. Stir untilentirely in solution. The temperature will rise to about-35 C. At 30-35 0., add 6.7 parts of bromine over a period of-2-3 hours. The solution becomesfviolet colored. *Ag itate at room temperature for 8-12 hours and pour out into 63 parts of cold water to decompose the aluminum chloride. Steamdistil'the mass until all the nitro-benz'ol has been-removed. The 1- methylamino-4-brom-anthraquinone is obtained in the-form of dark red crystals.

' In the examples given, iron chloride may be used in place"of' aluminumchloride and any of the known halogenating agents may be used in place of those specifically mentioned. In theclaims, where the term amino-anthraquinone compounds is used; it h is'intended to cover the amino compounds of 'anthraquinone in which the amino group is unsubstituted, substi: tuted, or which it may form part of a heterocyclic ring, which latter 'typeis illustrated in the examplesjby the azine and acridone compounds. Iclaimr 7' 7 I 1. In'the halogenation of amino-anthraquinone compounds, the step which 'comprises'carrying out the halogenation in nitrobenzene and a sufiicient amount of a'metal chloride'taken from thegroup consisting of aluminum chloride and iron chloride, to maintain the amino-anthraquinone compound and the resulting halogenation product in solution. I i

2.; In the halogenation of amino-anthraquinone compounds, the step which comprises carrying out the halogenation in a mixture-of nitrobenzene and aluminum chloride, suflicient aluminum chloride being usedv to maintain the amino-anthraquinone and the resulting halogenation product in solution. 3. In the halogenation of amino-anthraquinone compounds, the step which comprises carrying out the halogenation in nitrobenzene in which has been dissolved substantially one molecular quantity of aluminum chloride for each mol of the amino-anthraquinone' to be halogenated.

'4. In the halogenation of amino-anthraquinone compounds, the step which comprises carrying out'the'halogenation at relatively low temperatures in a solution of aluminum chloride in nitrobenzene, the amount: of nitrobenzene used being insufficient to maintain the amino-anthraquinone compound and the resulting chlorination product in solution at' 'the temperature of the reaction.

- WILLIAM DETTWYLER. 

